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Finding unambiguous evidence of dark matter interactions in a particle detector is a main objective of physics research. The liquid argon time projection chamber technique for the detection of Weakly Interacting Massive Particles (WIMP) allows sensitivities down to the so-called neutrino floor for high and low WIMP masses. Based on the successful operation of the DarkSide-50 detector, a new and more sensitive experiment, DarkSide-20k, was designed and is now under construction. A thorough understanding of the DarkSide-50 detector response to events classified as dark matter as well as all other interactions is essential for an optimal design of the new experiment. In this paper, we report on a particular set of events, for which scintillation-ionization signals are observed in association with signals from single or few isolated electrons. We identified and provided an interpretation for two event types in which electrons are produced via photoelectric effect on the cathode electrode and in the bulk liquid. Events with photoelectric emissions are observed in association with most interactions with large energy depositions in the detector. From the measured rate of these events, we determine the photo-ionization probability, or photoelectric quantum efficiency, of tetraphenyl butadiene (TPB) at wavelengths around 128 nm.